CN104815667A - Use of solid acid catalyst in synthesis of isobornyl acrylate - Google Patents
Use of solid acid catalyst in synthesis of isobornyl acrylate Download PDFInfo
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- CN104815667A CN104815667A CN201510153796.9A CN201510153796A CN104815667A CN 104815667 A CN104815667 A CN 104815667A CN 201510153796 A CN201510153796 A CN 201510153796A CN 104815667 A CN104815667 A CN 104815667A
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- acid catalyst
- solid acid
- ammonium
- acrylic acid
- isobornyl acrylate
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Abstract
The invention provides a use of a solid acid catalyst in synthesis of isobornyl acrylate. Acrylic acid and camphene undergo a reaction in the presence of the solid acid catalyst at a temperature of 30-90 DEG C for 2-10h to produce isobornyl acrylate, wherein a mole ratio of acrylic acid to camphene is 1.2: 1 to 3: 1 and a mass ratio of the solid acid catalyst to camphene is in a range of 0.01-0.25. The solid acid catalyst-based synthesis method is simple and easy, raw materials are cheap and easily available, acidity is high, cycle usage performances are good, acrylic acid-camphene reaction catalytic efficiency is high, isobornyl acrylate selectivity is high and a wide application prospect is obtained.
Description
Technical field
The present invention is specifically related to the application of a kind of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate.
Background technology
The esters of acrylic acid that isobornyl acrylate is made up of five-membered ring and hexatomic ring.Owing to there is double bond and special isobornyl thiocyanoacetate alkoxyl in its molecular structure, isobornyl acrylate is had advantages such as boiling point is high, volatility is little, good stability, therefore, have important application in industries such as adhesive, coating, mylar.
In recent years, isobornyl acrylate is in great demand, and according to statistics, the annual requirement of China's isobornyl acrylate is between 600 ~ 900 tons, and international market annual requirement is at 2500 ~ 3500 tons.Along with the expansion of isobornyl acrylate application study and the reduction of production cost, the application of following isobornyl acrylate will be widened further, and demand will increase further.
Isobornyl acrylate is mainly prepared by addition reaction with amphene by acid-catalyzed propylene acid.Acid is the important catalyst of a class, and the acid catalyst of current industrial application is liquid acid mostly, such as: sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, p-methyl benzenesulfonic acid etc.The acid catalyzed reaction of liquid belongs to homogeneous reaction, although catalytic activity is high, liquid acid etching apparatus, difficult and product separation, is difficult to recycling.
Have easily due to solid acid and product separation, be convenient to the advantages such as recycling, being subject to the extensive concern of academia and industrial quarters in recent years.The solid acid catalyst preparing isobornyl acrylate for catalysis reported at present comprises heteropllyacids, cationic ion-exchange resin class, zeolite molecular sieve class etc.US5399744 discloses a kind of method that Catalyzed by Phosphotungstic Acid prepares isobornyl acrylate, but the yield of isobornyl acrylate is low, and heteropoly acid dissolves as generating portion easy after catalyst reaction, not easily recycling.In addition, US5672733 and CN103304414A discloses the acid of strong acidic ion resin Amberlyst-15 catalyzing propone and reacts with amphene the method preparing isobornyl acrylate, but, easily side reaction is there is in this course of reaction, isobornyl acrylate poor selectivity, in addition, cationic ion-exchange resin class easily occurs swelling and broken in catalyse organic reaction process.
Summary of the invention
The object of the invention is to overcome in the reaction of existing solid acid catalysis acrylic acid synthesizing isobornyl thiocyanoacetate and easily side reaction occurs, the yield of isobornyl acrylate is low, poor selectivity, and the easy generating portion of solid acid catalyst is dissolved, swelling and broken problem.
For this reason, the invention provides the application of a kind of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate, solid acid catalyst is 30 ~ 90 in reaction temperature
ounder C condition, catalyzing propone acid is reacted with amphene and is prepared isobornyl acrylate in 2 ~ 10 hours, and the mol ratio of acrylic acid and amphene is 1.2:1 ~ 3:1, and solid acid catalyst quality is 1% ~ 25% of amphene quality;
Wherein, solid acid catalyst is with the ratio mixed dissolution of metal halide and water 1:5 ~ 1:100 in mass ratio, then adopt concentration be 5 ~ 20% alkali lye metal halide solution to be adjusted to behind pH=8 ~ 10 still aging 10 ~ 30 hours, adopt deionized water washing 3 ~ 10 times, 80 ~ 120
odry the solid 10 ~ 30 hours after washing in the baking oven of C, finally get ammonium salt and the pressed powder after oven dry in mass ratio 1:20 ~ 1:2 mix and be placed in 300 ~ 600
oroasting 3 ~ 15 hours in the Muffle furnace of C and obtaining.
Above-mentioned metal halide is two or more in tin tetrafluoride, butter of tin, tin tetrabromide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, zirconium tetrafluoride, zirconium chloride, zinc fluoride, zinc chloride, zinc bromide, ferric flouride, iron chloride, ferric bromide, aluminium chloride, aluminium bromide.
In the mixture of two or more metal halide above-mentioned, metal molar percentage is tin 0 ~ 20%, titanium 0 ~ 80%, zirconium 0 ~ 80%, zinc 0 ~ 20%, iron 0 ~ 20%, aluminium 0 ~ 20%.
Above-mentioned alkali lye is the one in NaOH, potassium hydroxide, ammoniacal liquor.
Above-mentioned ammonium salt is one or more in ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
Beneficial effect of the present invention:
(1) simple synthetic method preparing solid acid catalyst in the present invention is easy, and cheaper starting materials is easy to get, acid strong, recycles performance good.
(2) catalytic efficiency of this solid acid catalysis acrylic acid provided by the invention and amphene Reactive Synthesis isobornyl acrylate is high, and the yield of isobornyl acrylate and selective height, have broad application prospects.
Below with reference to accompanying drawing, the present invention is described in further details.
Accompanying drawing explanation
Fig. 1 is solid acid catalysis acrylic acid and amphene reaction equation in the present invention.
Fig. 2 adopts the acid of synthesis of solid acid-catalyzed propylene and amphene reactant liquor gas chromatogram in embodiment 2.
Fig. 3 be adopt in embodiment 2 synthesis of solid acid-catalyzed propylene acid with the decompression distillation of amphene reactant liquor after gas chromatogram.
Detailed description of the invention
Embodiment 1:
Easily side reaction is there is in order to overcome in the reaction of existing solid acid catalysis acrylic acid synthesizing isobornyl thiocyanoacetate, the yield of isobornyl acrylate is low, poor selectivity, the easy generating portion of solid acid catalyst is dissolved, swelling and broken problem, present embodiments provide the application of a kind of solid acid catalyst as shown in Figure 1 in acrylic acid synthesizing isobornyl thiocyanoacetate, solid acid catalyst is 30 ~ 90 in reaction temperature
ounder C condition, catalyzing propone acid is reacted with amphene and is prepared isobornyl acrylate in 2 ~ 10 hours, and the mol ratio of acrylic acid and amphene is 1.2:1 ~ 3:1, and solid acid catalyst quality is 1% ~ 25% of amphene quality.
Wherein, solid acid catalyst is with the ratio mixed dissolution of metal halide and water 1:5 ~ 1:100 in mass ratio, then adopt concentration be 5 ~ 20% alkali lye metal halide solution to be adjusted to behind pH=8 ~ 10 still aging 10 ~ 30 hours, adopt deionized water washing 3 ~ 10 times, 80 ~ 120
odry the solid 10 ~ 30 hours after washing in the baking oven of C, finally get ammonium salt and the pressed powder after oven dry in mass ratio 1:20 ~ 1:2 mix and be placed in 300 ~ 600
oroasting 3 ~ 15 hours in the Muffle furnace of C and obtaining.
The solid acid catalyst simple synthetic method adopted in the present invention is easy, and cheaper starting materials is easy to get, acid strong, recycles performance good, and catalyzing propone acid is high with amphene catalytic reaction efficiency, and the selective height of isobornyl acrylate, has broad application prospects.
Embodiment 2:
Take 3.506 g SnCl
45H
2o, 13.280 g TiCl
4, 2.703 g FeCl
36H
2o, 2.252 g ZnBr
2(metal molar percentage is 10%:70%:10%:10%), is dissolved in 500 mL water, abundant stirring and dissolving, add in solution concentration be 10% ammoniacal liquor be adjusted to pH=8.By the solution left standstill ageing after neutralization after 20 hours, deionized water is adopted to wash 5 times.Solid after washing is placed in baking oven 120
oc dries 20 hours.Pressed powder after oven dry fully grinds, cross 200 mesh sieves, and take a certain amount of ammonium phosphate (its quality and pressed powder mass ratio are 1:4), the powder after it being sieved with ground solid fully mixes.Mixed pressed powder is placed in Muffle furnace, 450
oc roasting 5 h, obtains solid acid catalyst.
Take 21.618 g acrylic acid, 27.246 g amphenes (mol ratio of acrylic acid and amphene is 1.5:1), the solid acid catalyst of 4.087 g synthesis and 2 g hydroquinones polymerization inhibitors, join in the there-necked flask of 500 mL, add thermometer and reflux condensing tube, open magnetic agitation and heating, setting reaction temperature is 50
oc, 6 hours reaction time, obtained isobornyl acrylate.
Infrared and the NH by pyridine
3-TPD characterizes obtained solid acid catalyst, shows that the solid acid catalyst synthesized is simultaneously containing Lewis acid position and Br nsted acid position, and containing a large amount of Br nsted strong acidic sites and super acids position.
To sampling after the cooling of obtained isobornyl acrylate, adopt gas chromatograph-mass spectrometric hyphenated technique, the gas chromatography retention time of combined standard product is to product qualitative analysis, adopt gas-chromatography to product quantitative analysis, as shown in Figure 2, retention time 8.7min is the chromatographic peak that isobornyl acrylate is corresponding.Obtain the isobornyl acrylate that purity is higher after decompression distillation, adopt gas-chromatography to carry out quantitative analysis, as shown in Figure 3, retention time 8.7min is the chromatographic peak that isobornyl acrylate is corresponding.Be 91.8% by can be calculated amphene conversion ratio, the selective of isobornyl acrylate is 95.6%, and obtaining isobornyl acrylate purity after decompression distillation is 92.5%.
Embodiment 3:
Take 5.25 g SnCl
45H
2o, 18.656 g ZrCl
4, 1.352 g FeCl
36H
2o(metal molar percentage is 15%:80%:5%), be dissolved in 1000 mL water, abundant stirring and dissolving, add in solution concentration be 20% NaOH be adjusted to pH=10; By the solution left standstill ageing after neutralization after 30 hours, deionized water is adopted to wash 10 times; Solid after washing is placed in baking oven 120
oCdry 30 hours; Pressed powder after oven dry fully grinds, cross 100 mesh sieves, and take a certain amount of ammonium sulfate and ammonium hydrogen sulfate mixture, its mixture quality and pressed powder mass ratio are 1:20, and the powder after it being sieved with ground solid fully mixes; Mixed pressed powder is placed in Muffle furnace, 600
oc roasting 15 h, obtains solid acid catalyst.
Take 21.618 g acrylic acid, 13.623 g amphenes (mol ratio of acrylic acid and amphene is 3:1), the solid acid catalyst of 0.1362 g synthesis and 2 g hydroquinones polymerization inhibitors, join in the there-necked flask of 500 mL, add thermometer and reflux condensing tube, open magnetic agitation and heating, setting reaction temperature is 30
oc, reaction time is 10 hours, after reaction terminates, sampling after cooling, adopt the gas chromatography retention time of gas chromatograph-mass spectrometric hyphenated technique combined standard product to product qualitative analysis, adopt gas-chromatography to product quantitative analysis, after decompression distillation, obtain the isobornyl acrylate that purity is higher, adopt gas-chromatography to carry out quantitative analysis.Calculating amphene conversion ratio is 83.6%, and the selective of isobornyl acrylate is 91.8%, and obtaining isobornyl acrylate purity after decompression distillation is 93.3%.
Embodiment 4:
Take 7.012 g SnCl
45H
2o, 13.280 g TiCl
4, 2.414 g AlCl
36H
2o(metal molar percentage is 20%:70%:10%), be dissolved in 500 mL water, abundant stirring makes it all dissolve, add in solution concentration be 5% potassium hydroxide be adjusted to pH=8, by the solution left standstill ageing after neutralization after 15 hours, adopt deionized water to wash 3 times, the solid after washing is placed in baking oven 100
oCdry 15 hours; Pressed powder after oven dry fully grinds, cross 200 mesh sieves, take a certain amount of ammonium hydrogen sulfate (its quality and pressed powder mass ratio are 1:2), powder after it being sieved with ground solid fully mixes, and mixed pressed powder is placed in Muffle furnace, 500
oc roasting 10 h, obtains solid acid catalyst.
Take 21.618 g acrylic acid, 34.058 g amphenes (mol ratio of acrylic acid and amphene is 1.2:1), the solid acid catalyst of 8.515 g synthesis and 2 g hydroquinones polymerization inhibitors, join in the there-necked flask of 500 mL, add thermometer and reflux condensing tube, open magnetic agitation and heating, setting reaction temperature is 90
oc, reaction time is 2 hours, after reaction terminates, sampling after cooling, adopt the gas chromatography retention time of gas chromatograph-mass spectrometric hyphenated technique combined standard product to product qualitative analysis, adopt gas-chromatography to product quantitative analysis, after decompression distillation, obtain the isobornyl acrylate that purity is higher, adopt gas-chromatography to carry out quantitative analysis.Calculating amphene conversion ratio is 78.9%, and the selective of isobornyl acrylate is 88.4%, and obtaining isobornyl acrylate purity after decompression distillation is 91.8%.
The metal halide used in above-described embodiment can be replaced by two or more in tin tetrafluoride, butter of tin, tin tetrabromide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, zirconium tetrafluoride, zirconium chloride, zinc fluoride, zinc chloride, zinc bromide, ferric flouride, iron chloride, ferric bromide, aluminium chloride, aluminium bromide.
The ammonium salt used in above-described embodiment can be replaced by one or more in ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
In sum, the catalytic efficiency of this solid acid catalysis acrylic acid provided by the invention and amphene Reactive Synthesis isobornyl acrylate is high, and the yield of isobornyl acrylate and selective height, have broad application prospects.
More than exemplifying is only illustrate of the present invention, does not form the restriction to protection scope of the present invention, everyly all belongs within protection scope of the present invention with the same or analogous design of the present invention.
Claims (5)
1. the application of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate, is characterized in that: solid acid catalyst is 30 ~ 90 in reaction temperature
ounder C condition, catalyzing propone acid is reacted with amphene and is prepared isobornyl acrylate in 2 ~ 10 hours, and the mol ratio of acrylic acid and amphene is 1.2:1 ~ 3:1, and solid acid catalyst quality is 1% ~ 25% of amphene quality;
Wherein, solid acid catalyst is with the ratio mixed dissolution of metal halide and water 1:5 ~ 1:100 in mass ratio, then adopt concentration be 5 ~ 20% alkali lye metal halide solution to be adjusted to behind pH=8 ~ 10 still aging 10 ~ 30 hours, adopt deionized water washing 3 ~ 10 times, 80 ~ 120
odry the solid 10 ~ 30 hours after washing in the baking oven of C, finally get ammonium salt and the pressed powder after oven dry in mass ratio 1:20 ~ 1:2 mix and be placed in 300 ~ 600
oroasting 3 ~ 15 hours in the Muffle furnace of C and obtaining.
2. the application of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate as claimed in claim 1, is characterized in that: described metal halide is two or more in tin tetrafluoride, butter of tin, tin tetrabromide, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, zirconium tetrafluoride, zirconium chloride, zinc fluoride, zinc chloride, zinc bromide, ferric flouride, iron chloride, ferric bromide, aluminium chloride, aluminium bromide.
3. the application of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate as claimed in claim 2, it is characterized in that: in the mixture of two or more metal halide described, metal molar percentage is tin 0 ~ 20%, titanium 0 ~ 80%, zirconium 0 ~ 80%, zinc 0 ~ 20%, iron 0 ~ 20%, aluminium 0 ~ 20%.
4. the application of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate as claimed in claim 1, is characterized in that: described alkali lye is the one in NaOH, potassium hydroxide, ammoniacal liquor.
5. the application of solid acid catalyst in acrylic acid synthesizing isobornyl thiocyanoacetate as claimed in claim 1, is characterized in that: described ammonium salt is one or more in ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium nitrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902388A (en) * | 2018-04-04 | 2020-11-06 | 大阪有机化学工业株式会社 | Composition containing isobornyl (meth) acrylate and preparation method thereof |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN114702387A (en) * | 2022-04-18 | 2022-07-05 | 江西美龙达新材料有限公司 | Isobornyl (meth) acrylate and process for its preparation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111902388A (en) * | 2018-04-04 | 2020-11-06 | 大阪有机化学工业株式会社 | Composition containing isobornyl (meth) acrylate and preparation method thereof |
| CN111902388B (en) * | 2018-04-04 | 2024-02-20 | 大阪有机化学工业株式会社 | Isobornyl (meth) acrylate-containing composition and method for producing same |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN112142593B (en) * | 2020-08-28 | 2021-07-06 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN114702387A (en) * | 2022-04-18 | 2022-07-05 | 江西美龙达新材料有限公司 | Isobornyl (meth) acrylate and process for its preparation |
| CN114702387B (en) * | 2022-04-18 | 2024-02-27 | 江西美龙达新材料有限公司 | Isobornyl (meth) acrylate and preparation method thereof |
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